Removal of salts in the manufacture of phenolic compound

ABSTRACT

There is provided a process for the manufacture of phenolic compounds by separating a neutralized aralkyl hydroperoxide cleavage mass stream containing salts of neutralization into a crude ketone stream and a crude phenolic stream containing the salts of neutralization; separating the crude phenolic stream into a concentrated phenolic-rich stream, enriched in phenolic compounds, and a crude phenolic bottoms stream enriched in tars and alpha methyl styrene dimers, each compared to the crude phenolic stream, said crude phenolic bottoms stream containing salts of neutralization; to the crude phenolic bottoms stream, adding water and a diluent composition, thereby forming a phase separable crude phenolic bottoms stream, said diluent composition comprised of hydrocarbons phase compatible with the crude phenolic bottoms stream and having a combined density lower than the density of the crude phenolic bottoms stream; separating the separable crude phenolic bottoms stream into a hydrocarbon phase and an aqueous phase containing salts of neutralization; whereby the amount of salts of neutralization in the hydrocarbon phase is reduced compared to the amount of salts of neutralization present prior to separation.

FIELD OF THE INVENTION

1. The present invention relates to a process for separating productscontained in an alkyl hydroperoxide cleavage mass, and in particular, toa process for the removal of salts of neutralization present in acleavage mass for the manufacture of phenol.

BACKGROUND OF THE INVENTION

2. In general, phenol is manufactured by oxidizing an alkyl substitutedaromatic compound, such as cumene, to form the hydroperoxide derivativethereof, followed by cleavage of the hydroperoxide with a mineral acidsuch as sulfuric acid to form a cumene hydroperoxide cleavage mass. Thecleavage mass generally contains species such as phenol, acetone,α-methyl styrene (AMS), cumene, cumyl phenol (CP), dimethylbenzylalcohol (DMBA), acetophenone (AP), AMS dimers (AMSd), tars and heavies,and mineral acid such as sulfuric acid. Prior to separating out thedifferent species and recovering acetone and phenol, the cleavage massis neutralized with a caustic, such as sodium hydroxide, to prevent theacidic cleavage mass from corroding downstream equipment. Much of thesalt is separated and removed from the process in a wash/phaseseparation step prior to feeding the partially or wholly neutralizedcleavage mass to a splitter and further purification columns However, asignificant quantity of salt remains in the cleavage mass entering thesplitter, and this quantity of salt becomes more concentrated as thestream passes from one purification column to the next.

3. In the course of making phenol, the fully or partially neutralizedcleavage mass passes through several distillation and purificationcolumns to ultimately form a stream of heavy by-products. The heavyby-product stream may be subject to cracking, and the bottoms of thecracker are usually incinerated. The heavy hydrocarbon by-product streamfeeding a cracker or furnace, however, contains a high concentration ofthe salts of neutralization, typically sodium sulfate. The saltsremaining after the wash/phase separation step are carried into thesplitter, which separates out ketone as an overhead from phenol as aphenol bottoms stream, into the phenol bottoms stream and into furtherdownstream equipment through the bottoms stream of each purificationcolumn, all the way to the cracker or furnace. It is in the cracker andfurnace, and in the reboiler for the cracker, where the salts ofneutralization settle and are no longer carried through. The settling ofthe salts in the cracker, reboiler, and furnaces causes operatingproblems, requiring intermittent shut down to clean the equipment orreplace parts. The salts also degrade the value of a tarry mass as fuelfor burning. Therefore, it is highly desirable to remove as much salt aspossible prior to feeding a cracker or furnace.

4. Many methods have been proposed for removing salts of neutralizationin the manufacture of phenol. One such method, disclosed in U.S. Pat.No. 4,328,377, involves feeding a neutralized cleavage mass to amulti-tray (20 or more) splitter, separating out the ketone as anoverhead from a bottom fraction comprised of a crude phenol stream, andrecovering the phenol, wherein a liquid layer located near or below thecleavage mass feed site but above the bottoms is withdrawn from thesplitter column, phase separating the liquid layer into an oil layer andan aqueous layer containing the salts of neutralization, and recyclingthe oil layer back to the splitter column at a site below the liquidlayer withdrawal site. To enhance the ability of the liquid layer tophase separate, a hydrocarbon having a lower boiling point than phenoland a specific gravity difference of at least 0.03 is added to theliquid layer.

5. A disadvantage of this process is that large quantities of liquidlayer must be removed and processed to sufficiently reduce the amount ofsalt to the desired level. For example, for every 100 parts by weightper hour of cleavage mass fed to the mutli-tray splitter, 127 parts byweight per hour of a liquid sidedraw was processed in a phase separator.Treating such large amount of liquid requires adding and processingcorresponding large quantities of water, and adding large quantities oflower specific gravity hydrocarbon, processing large amounts of oillayer, and increasing the volume of the phase separation vessel. Itwould be desirable to discharge the salts of neutralization from theprocess by feeding a phase separator with a small amount of hydrocarbon,discharging low amounts of water containing the salts of neutralizationfrom the process while effectively removing at least 80% of the salts ofneutralization from the process, using low amounts of lower densityhydrocarbon to enhance phase separation, concentrating the salt in apurge stream discharged from a phase separator to high levels, and/oremploying a smaller phase separation vessel. It would also be desirableto employ a process for manufacturing phenol where the amount of wateror lower density hydrocarbon lost from the process is minimized oreliminated

SUMMARY OF THE INVENTION

6. In one embodiment of the invention, there is provided a process forthe manufacture of phenolic compounds comprising:

7. a) separating a neutralized aralkyl (aryl alkyl or alkyl aryl)hydroperoxide cleavage mass stream containing salts of neutralizationinto a crude ketone stream and a crude phenolic stream containing thesalts of neutralization;

8. b) separating the crude phenolic stream into a concentratedphenolic-rich stream, enriched in phenolic compounds, and a crudephenolic bottoms stream enriched in tars and alpha methyl styrenedimers, each compared to the crude phenolic stream, said crude phenolicbottoms stream containing salts of neutralization;

9. c) to the crude phenolic bottoms stream, adding water and a diluentcomposition, thereby forming a phase separable crude phenolic bottomsstream, said diluent composition comprised of a hydrocarbon phasecompatible with the crude phenolic bottoms stream and having a combineddensity lower than the density of the crude phenolic bottoms stream;

10. d) separating the separable crude phenolic bottoms stream into ahydrocarbon phase and an aqueous phase containing salts ofneutralization;

11. whereby the amount of salts of neutralization in the hydrocarbonphase is reduced compared to the amount of salts of neutralizationpresent prior to separation.

12. In another embodiment of the invention, there is provided a processfor the manufacture of phenolic compounds comprising wholly or partiallyneutralizing an aralkyl hydroperoxide cleavage mass feed containing anacid and having a pH of less than 6 in neutralization zone, therebyforming an aqueous neutralized aralkyl hydroperoxide cleavage masscontaining salts of neutralization, subsequently separating said aqueousneutralized aralkyl hydroperoxide cleavage mass into an aqueous streamand a neutralized aralkyl hydroperoxide cleavage mass stream containinga smaller amount of salts than in the aqueous stream, subsequentlyseparating the aralkyl hydroperoxide cleavage mass into a crude ketonestream and a crude phenolic stream containing the salts, separating saidcrude acetone stream into a concentrated ketone rich stream and a crudeketone bottoms stream, separating said crude phenolic stream into aconcentrated phenolic-rich stream and a crude phenolic bottoms stream,and ultimately separating from the crude phenolic bottoms stream a lightends stream and a tarry stream containing an amount of salts reduced byat least 90% of the amount of salts contained in the crude phenolicbottoms stream, and recycling at least a portion of said crude ketonebottoms stream and at least a portion of said light ends stream as feedsto said aralkyl hydroperoxide cleavage mass, said aqueous neutralizedaralkyl hydroperoxide cleavage mass, or to both.

13. In yet another embodiment of the invention, there is provided acomposition comprising at least 40 wt. % water, less than 20 wt. %phenolic compounds, alkali metal salts in an amount of at least 1.5 wt.%, phenolic tars, and α-methyl styrene dimers, wherein the volume ratioof water to all ingredients in said composition other than water isbetween 1:1 to about 3:1.

14. In yet a further embodiment of the invention, there is provided aprocess for removing salts of neutralization present in a neutralizedaralkyl hydroperoxide cleavage mass comprising removing 80 wt. % or moreof said salts from said cleavage mass through one or more aqueousstreams discharged and purged from said process, the combined flow rateof all aqueous purge stream(s) containing the salts being less than 5parts by weight per hour based on a flow rate of 100 parts by weight perhour of the cleavage mass fed to a means for separating said cleavagemass into a crude ketone stream and a crude phenolic stream.

15. There is also provided an embodiment for manufacturing phenoliccompounds comprising feeding a neutralized aralkyl hydroperoxidecleavage mass containing salts of neutralization to a splitter,separating acetone and phenol from said cleavage mass in the splitter,removing all or a portion of the phenol from the splitter, followed byfeeding said all or a portion of said phenol to a phase separationvessel having a volume of 5000 gallons or less, based on 100 parts byweight per hour of cleavage mass feed to the splitter, and removing atleast 80 wt. % of the salts of neutralization from said phenol.

16. In another embodiment, there is provided a process for removingsalts of neutralization, comprising feeding an aralkyl hydroperoxidecleavage mass containing salts of neutralization to a splitter,separating acetone from a crude stream of phenol in said splitter,followed by feeding a portion or all of said crude phenol stream to aphase separator as a feed comprising hydrocarbons, water, and salts ofneutralization, the total amount of hydrocarbon feed from any source tosaid separator being less than 10 parts by weight per hour, based on 100parts by weight per hour of said cleavage mass fed to the splitter,wherein at least 80 wt. % of the salts of neutralization are removedfrom the crude phenol stream.

17. In another embodiment of the invention, there is provided a processfor removing salts of neutralization from an aralkyl hydroperoxidecleavage mass containing salts of neutralization comprising separatingacetone from said cleavage mass, followed by purging the salts ofneutralization in an aqueous purge stream comprising at least 3 wt. % ofthe salts of neutralization and at least 90 wt. % water, based on theweight of the purge stream.

18. In a further embodiment of the invention, there is provided aprocess for making phenol comprising feeding an aralkyl hydroperoxidecleavage mass containing salts of neutralization into a splitter andseparating the cleavage mass in the splitter into a ketone stream and aphenol stream containing the salts, optionally concentrating the phenolstream by further distillation, and forming a phase separablehydrocarbon stream from said phenol stream comprising adding a netamount of water of 5 parts by weight per hour or less to the phenolstream, based on 100 parts by weight per hour of cleavage mass fed tothe splitter, phase separating the phase separable hydrocarbon streaminto an aqueous stream and a hydrocarbon stream, and discharging aportion or all of the aqueous stream from the process as an aqueouspurge stream, wherein at least 80 wt. % of the salts of neutralizationpresent in the cleavage mass entering the splitter are removed throughsaid purge stream.

19. The various features of the invention are described in furtherdetail below.

BRIEF DESCRIPTION OF THE DRAWINGS

20.FIG. 1 is a process flow diagram of that portion of the process forthe separation of products contained in an alkyl hydroperoxide cleavagemass.

DETAILED DESCRIPTION OF THE INVENTION

21. A more detailed understanding of the invention may be had byreference to FIG. 1, which illustrates features of the invention as wellas more preferable embodiments of the invention.

22.FIG. 1 is an illustration of a process directed towards separatingthe by-products contained in a cumene hydroperoxide cleavage mass intostreams of acetone, phenol, α-methyl styrene (AMS), cumene, aqueousstreams containing salts of neutralization such as NaSO₄, cumyl phenol(CP), dimethylebenzyl alcohol (DMBA), acetophenone (AP), AMS dimers(AMSd), and tars and heavies. Those of ordinary skill in the art willappreciate that other vessels not depicted in FIG. 1 may be included inthe process of the invention, such as further distillation columns foradditional purification, additional phase separators, coolers, heatexchangers, pumps, and storage vessels where desired. Thus, otherpurification columns may be introduced prior to or after each successivedescription where products contained in a particular stream areseparated. For example, describing the separation of a light ends streamfrom a tarry stream in a crude phenol bottoms stream does not restrictthe inclusion of any number of prior purification columns introduced tofurther purify the crude phenol bottoms stream prior to the point atwhich a tarry stream is extracted.

23. Turning to FIG. 1, while reference may be had to a cumenehydroperoxide cleavage mass flowing through line (2), the invention alsoincludes processing an aralkyl hydroperoxide cleavage mass. The aralkylhydroperoxide used in the process of this invention includes compoundsrepresented by formulas 1 and 2 below:

24. wherein Ar represents an aromatic ring, preferably a phenyl ring,and R1, R2, R3 and R4 independently represent a lower linear or branchedalkyl group having 1-4 carbon atoms. Specific examples of the aralkylhydroperoxide are cumene hydroperoxide, p-cymene hydroperoxide, m-cymenehydroperoxide, sec-butylbenzene hydroperoxide, p-ethylisopropylbenzenehydroperoxide, isopropylnaphthalene hydroperoxide, m-diisopropylbenzenedihydroperoxide and p-diisopropylbenzene dihydroperoxide. Cumenehydroperoxide, p-cymene hydroperoxide and m-cymene hydroperoxide arepreferred. Cumene hydroperoxide is most preferred.

25. The cleavage mass is acidic due to the addition of a mineral acid,such as sulfuric acid, to the aralkyl hydroperoxide to effect cleavageof the hydroperoxide into a ketone compound, such as acetone, and aphenolic compound, such as phenol, along with the other byproducts notedabove. Examples of the mineral acid used to cleave the hydroperoxideinto a phenolic compound and a ketone compound include sulfuric acid,hydrochloric acid, phosphoric acid and mixtures of these. Sulfuric acidis the most common agent used.

26. The phenolic compound, which is one of the desired acid cleavageproducts of the process, is represented by the formula Ar—OH or HO—Ar—OHcorresponding to formula (1) or (2). Specific examples include phenol,p-cresol, m-cresol, ethylphenol, naphthol, hydroquinone and resorcinol.Phenol, p-cresol and m-cresol are preferred, and phenol is mostpreferred.

27. The ketone compound, another desirable acid cleavage byproduct, isexpressed by formula 3:

28. Examples include acetone and methyl ethyl ketone, preferablyacetone.

29. Any known method can be employed to cleave the hydroperoxide with amineral acid. Industrially, the cleavage reaction is usually performedin the presence of a hydrocarbon solvent. An aromatic hydrocarbon ispreferred as the hydrocarbon solvent, and specific examples includebenzene, toluene, xylene, cumene, cymene, ethylbenzene, phenol,diisopropylbenzene, butylbenzene, alpha-methylstyrene andisopropenyltoluene. The temperature of the acid cleavage is notparticularly restricted. Advantageously, it is generally about 50° C. toabout 100° C., preferably about 70° C. to about 90° C. Generally, theamount of the mineral acid is 0.005 to 2 parts by weight, preferably0.01 to 0.1 parts by weight, per 100 parts by weight of thehydroperoxide to be cleaved.

30. The mineral acid contained in the reaction mixture obtained by theacid cleavage of the hydroperoxide is then neutralized or removed. Theparticular method of neutralization is not limited. The acidic cleavagemass stream is fed to a neutralizer (10), where residual sulfuric acidis neutralized either partially or wholly by addition of a causticthrough line (13). By a neutralized cleavage mass is meant a cleavagemass which is partially or wholly neutralized. Neutralization of theacid cleavage mixture of the hydroperoxide can be performed by anydesired known method. The caustic may be added to line (2) prior toentry into neutralizer (10) or directly to the neutralizer (10). Atypical caustic is an aqueous sodium hydroxide stream and/or sodiumphenolate.

31. The salt formed as a result of the neutralization of the acidcleavage needs not always to be separated and removed from the cleavagemass. However, it is common to remove a portion of the salts prior tofeeding the cleavage mass to the splitter (30). Methods includecontacting the acid cleavage mixture with an aqueous solution of astrong alkali such as sodium hydroxide or sodium phenolate and thenoptionally removing the water layer by in a phase separator; orcontacting the acid cleavage mixture with an aqueous solution of astrong alkali such as sodium hydroxide, removing the aqueous layerthrough phase separation, followed by washing the hydrocarbon oily layerwith water to remove more salt; or a method where the neutralizedcleavage mass is filtered to remove the salt precipitated in solid form.

32. In a particular embodiment of the invention, reference may be had tothe design depicted in FIG. 1. In the neutralizer (10), the sulfuricacid present in the hydrocarbon phase of the cleavage mass forms aNa₂SO4 salt in the aqueous phase which leaves the neutralizer throughline (14). A portion of the salty aqueous stream may be recirculatedback to the neutralizer through line (14), and a portion may bedischarged through line (15). The conditions within the neutralizer (10)may vary depending upon the number of neutralizers, wash drums, andphase separators one may employ, but typical conditions are to maintainthe pH between 5 and 8 at 1 or more atmospheres and at a temperatureranging from 35° C. to 55° C. Other conditions and equipment, such asthose specified in U.S. Pat. Nos. 5,510,543; 3,931,339; 4,262,150; and4,262,151 are also suitable, and each are herein incorporated byreference in full. For example, if desired, the cleavage mass may beonly neutralized up to a pH within the range of 4-5.

33. The hydrocarbon phase leaves the neutralizer (10) through line (11)and is fed into a wash drum (20) through line (12). In addition toadjusting the pH back to a range of 5-7, the wash drum washes theresidual Na₂SO₄ salts remaining in the hydrocarbon phase with water, aportion of which is discharged and a portion of which may berecirculated back to the wash drum (20) by joining with line (11).

34. In spite of the many efforts at effecting a substantially completeremoval of salts, residual amounts of salts remain within thehydrocarbon stream. The amount of salt left in a composition ofneutralized aralkyl hydroperoxide cleavage mass prior to entering thesplitter will vary depending upon the degree of neutralization and theefficiency of the separation techniques used to remove the salt in aphase separation and/or wash step. The process of the invention can beused to remove salt at any level. Typical amounts of salt in aneutralized cleavage mass range from 1000 ppm to 10,000 ppm. The amountof salt is generally reduced within a range of 300 ppm to severalthousand ppm salt. In the process of the invention, the amount of saltcan be reduced to even smaller quantities of salt, in the range of 25ppm to 300 ppm, preferably from 25 ppm to 120 ppm.

35. The neutralized and optionally washed cumene hydroperoxide cleavagemass is fed to the splitter (30) through line (21) where the cleavagemass is separated through, for example, distillation, into a crudephenolic stream and a crude acetone stream. The crude acetone streamremoved from the splitter at the overhead through line (31) is rich inacetone, meaning that acetone is the predominant species in the streamby weight. Small amounts of water and other higher boiling compoundssuch as AMS, cumene, some aldehydes, and un-neutralized organic acidsmay also be present in the crude acetone stream. Some of the lighterboiling impurities, such as other aldehydes, may optionally be removedfrom the composition by distillation and optionally recycled back alongwith acetone caught up in the overhead to a cleavage zone where thearalkyl hydroperoxide is cleaved.

36. Whether or not distilled, the crude acetone stream is fed throughline (31) ultimately to an acetone finishing column (40) where the crudeacetone stream is separated by distillation into a concentrated acetonestream enriched in acetone over the amount of acetone present in thecrude acetone stream and into a crude acetone bottoms stream. Theconcentrated acetone stream is removed from the finishing column (40)through line (41), while the crude acetone bottoms stream is removed atthe bottom of the column (40) through line (42). Optionally, caustic maybe added to the finishing column (40) to react the aldehyde to heaviercompounds, thereby facilitating removal by distillation.

37. The crude acetone bottoms stream is comprised of water, organicacids, AMS, and cumene. To separate water from the hydrocarbons in thecrude acetone bottoms stream, it is useful to feed the stream to a phaseseparator (50) wherein water and the salts of the organic acid areseparated and discharged as an aqueous phase through line (52) from thehydrocarbon phase, which leaves the separator (50) through line (51).Optionally, a portion of the aqueous phase discharged from separator(50) may be recycled back to line (1) through line (52A) to reduce theamount of fresh water feed that is added to the phase separator/washdrum. The other portion is sent to treatment for dephenolation throughline (52B).

38. The crude acetone bottoms stream in line (51) from which water hasoptionally been removed is comprised of AMS, cumene, and otherhydrocarbon compounds having boiling points lower than phenol. Part ofthe crude acetone bottoms stream, whether processed through the phaseseparator (50) or not, is used to feed the neutralizer (10) through line(53) in order to facilitate phase separation between the cleavage massand water. The amount of crude acetone bottoms stream fed to theneutralizer (10) through line (53) may range anywhere from 5 wt. % to 40wt. % based on the weight of the cleavage mass stream. The crude acetonebottoms stream may be fed and mixed into line (1) or may be fed directlyinto the neutralizer. Optionally, the crude acetone bottoms stream befed to the wash drum (20) as well.

39. Another portion of the crude acetone bottoms stream from the acetonefinishing column (40) or from the phase separator (50) may be fed as adiluent to line (62) described further below in greater detail.

40. The crude phenol stream exits the bottom of the splitter (30)through line (32). The predominant species in the crude phenol stream isphenol, usually in amounts exceeding 85 wt. % based on all ingredientsin the crude phenol stream. The salts of neutralization (Na₂SO₄) presentin the cumene hydroperoxide cleavage stream in line (21) pass throughthe splitter (30) into the crude phenol stream. Accordingly, the amountof salts usually ranges from be 80-230 ppmw based on the weight of allingredients in the crude phenol stream as measured at line (32), or from0.05 to 0.3 wt. % based on the weight of all ingredients in the crudephenol stream as measured at line (62). Other ingredients present in thecrude phenol stream include AP, CP, AMSd, DMBA, and tars and heavies.

41. A substantial amount of the phenol present in the crude phenolstream is removed by feeding the stream in line (32) into a crude phenolcolumn (60) where phenol is separated by distillation into aconcentrated phenol rich stream which is enriched in the weightpercentage of phenol compared to the weight percentage of phenol presentin the crude phenol stream, and into a crude phenolic bottoms streamenriched in tars and AMSd compared to the weight percent of tars andAMSd present in the crude phenol stream. The concentrated phenol richstream exits the column (60) through line (61) for finishing, while thecrude phenol bottoms stream exits the bottoms of the column (60) throughline (62).

42. The typical composition of the crude phenol bottoms stream is asfollows: Phenol: 15-35 wt. % AP: 10-25 wt. % DMBA: 2-8 wt. % CP: 15-25wt. % AMSd: 4-15 wt. % Tars/Heav: 12-25 wt. % Salts: 0.05-0.3 wt. %

43. To the crude phenol bottoms stream is added water and a diluentcomposition which is phase compatible with the crude phenolic bottomsstream in order to form a phase separable crude phenolic bottoms stream.For measurement purposes only, a stream becomes phase separable when astanding batch, without agitation, phase separates into a hydrocarbonphase and an aqueous phase containing at least 80 wt. % of salts ofneutralization without agitation within a period of 0.5 hours or less. Aphase separable crude phenolic bottoms stream is one in which ahydrocarbon phase and an aqueous phase containing at least about 80 wt.% of the salts of neutralization, as measured by allowing the stream tostand without agitation, can be separated in less than one hourresidence time.

44. The hydrocarbon portion of the diluent stream consisting of allhydrocarbons in the diluent stream have a combined lower density thanthe density of the crude phenolic bottoms stream under the conditionsexisting in the bottoms phase separator (80). While the diluent streamcan be derived from any source, it is advantageous to recycle a portionof the crude acetone bottoms stream comprised of cumene and AMS throughline (54) into the crude phenol bottoms stream in line (62). Thehydrocarbons in the diluent stream in line (54) comprised of cumene andAMS flow through the process ultimately into line (102) from thedistillation in the rectifier (100), and fed to the neutralizer (10),thereby closing the loop on the flow of the hydrocarbon portion of thediluent stream through the process with minimal discharge.

45. As an example, the density of the crude phenol bottoms stream may beon the order of 54-58 pcf at temperatures ranging from 180-210° C. andat pressures sufficient to keep the stream in liquid state. Althoughphenol has a higher density than water, it is also readily miscible withwater, rendering it difficult to obtain satisfactory phase separationbetween the hydrocarbon phase and the aqueous phase in a phaseseparation operation designed to remove the salts of neutralization.Accordingly, a hydrocarbon diluent having a lower density that thedensity of the crude phenol bottoms stream is added to enhance phaseseparation between the hydrocarbon and aqueous phase. This method ofenhancing phase separation is more effective at removing salts than amethod of increasing the salt concentration because by increasing thesalt concentration, the amount of salt distributed into the hydrocarbonphase is increased and the effectiveness of the unit operation isreduced.

46. Diluents which are phase compatible and readily miscible withphenol, have a lower density than phenol, and which are phaseincompatible with water under the operating conditions of the phaseseparator are preferred. Such diluents will attract solubilized phenolfrom the aqueous phase into the hydrocarbon phase. A diluent compositionhaving a combined hydrocarbon density of 51-53.5 pcf comprised of 60-90wt. % cumene, 10-30 wt. % of AMS, and optionally less than 10 wt. % ofother hydrocarbons and no water is but one example, but is a preferredcomposition because it is readily obtainable as an extract from theacetone finishing operation. Optionally, if desired, the diluentcomposition may be recycled directly from the acetone finishing column(40) to line (62) without first removing water. Another example of asuitable diluents include a stream of cumene or a stream of AMS, each asa fresh feed or derived from any source in the process.

47. While a diluent hydrocarbon stream having a lower density than thecrude phenol bottoms stream must be added to obtain satisfactory phaseseparation, the density difference need not be large. Although theinvention is not restricted to a particular density difference, anadvantage of the invention is that the hydrocarbon phase may beeffectively separated from the aqueous phase in the phase separator (80)when the density difference between the two is only 1-2 pcf. Thisadvantage is achieved due to the low percentage of phenol present in thecrude phenolic bottoms stream. A stream comprised of 85 wt. % or morephenol would require the use of a diluent having a larger density deltato effectively phase separate the aqueous phase due to the readymiscibility between phenol and water.

48. An additional advantage to the invention is that the volume amountof diluent needed to provide a phase separable stream is low compared tothe volume of diluent that would be needed if one attempted to create aphase separable stream from a stream exiting the splitter (30) as eithera side-draw or from a bottoms, as in line (32). Since a large volume ofcompounds in the cleavage stream in line (21) are removed in thesplitter (30) through line (31), and the volume of the crude phenolstream in line (32) is reduced further by removal of phenol through thecrude phenol column (60) into line (61), the process provides theadvantage of needing only low amounts of diluent to effect satisfactoryphase separation.

49. Specifically, for every 100 part by weight per hour of cleavage massfed through line (21) into the splitter (30), less than 3 parts byweight per hour of diluent is advantageously needed to make a phaseseparable crude phenol bottoms stream, preferably less than 2, and evenas little as 1.5 parts by weight per hour or less, each based on 100parts by weight per hour of aralkyl hydroperoxide cleavage mass streamand discounting any water present in the phase separable crude phenolbottoms.

50. The amount of diluent added relative to the amount of crude phenolbottoms stream is sufficient to phase separate the hydrocarbon phasefrom the aqueous phase. While there is no upper limit, the more diluentadded, the higher the loading of material through downstream equipmentwhich must be processed and handled. Suitable weight ratios of diluentcomposition to crude phenol bottoms composition are at least 0.15:1,more preferably 0.3:1, most preferably from 0.45-0.6:1. The specificamount of diluent is balanced between keeping the loading factor lowwhile providing sufficient diluent to efficiently phase separate.

51. A diluted crude phenolic bottoms stream composition may comprise:AMS: 3-10 wt. % Cumene: 10-40 wt. % Phenol: 5-25 wt. % AP: 7-20 wt. %DMBA: 1-5 wt. % CP: 7-20 wt. % AMSd: 3-10 wt. % Tars/Heav: 6-20 wt. %Salts: 0.05-0.25 wt. %

52. Since relatively small amounts of feed to the phase separator areeffective to remove 80 wt. % or more of salts of neutralization, theoverall volumetric hydrocarbon flow to the phase separator (80) is alsovery low. By hydrocarbon is meant any compound in a stream other thatwater. In particular, the flow rate of all hydrocarbons to the phaseseparator from any source need only be on the order of less than 10,preferably less that 7, more preferably 6, most preferably 5 or lessparts by weight per hour based on 100 parts by weight per hour of totalcleavage mass feed to the splitter (30), to effectively separate anddischarge at least 80 wt. %, more preferably at least 90 wt. % of thesalts of neutralization from the phase separator into a salty aqueouspurge stream.

53. In addition to a diluent stream, water is added to the crude phenolbottoms stream as the additional ingredient to further enhance theability of the crude phenol bottoms stream to phase separate. Asdepicted in FIG. 1, water is added to the diluted crude phenol bottomsstream in line (63) through line (82) after the diluent has been added,to make the phase separable crude phenol bottoms stream. The amount ofwater should be kept as low as possible to concentrate the salts andavoid loading the system with excess water and avoid loss of phenol tothe aqueous phase since phenol and water are miscible, while on theother hand, facilitating removal of salts from the hydrocarbon phase byincreasing the difference in density between the phases. It is withinthe ordinary skill to acquire an optimal range of water balanced betweenenhancing phase separation and avoiding an excessive loss of phenol intothe aqueous stream.

54. In general, the amount of water by volume is in excess over theamount of hydrocarbon by weight. A volume ratio of water to hydrocarbonin the phase separable crude phenol bottoms stream ranging from 1.1:1 to3:1 is suitable, with a ratio of about 1.5:1 to 2.5:1 being morepreferred, and a ratio of about 2:1 being most preferred.

55. Water can be added as a liquid or vapor, preferably as a liquid.Water can also be added as a fresh stream or as a recycle streamoriginating from the bottoms phase separator (80), preferably thelatter. Water may be added before, simultaneous to, or after the diluentis added. In one embodiment, water is added to the diluted crude phenolbottoms stream through line (82) originating from a bottoms phaseseparator (80). A typical non-limiting example of the water streamcomposition comprises 90-95 wt. % water, 3-7 wt. % salts ofneutralization, and 0.5-3 wt. % of phenol.

56. In another advantageous embodiment of the invention, there isprovided a process for making a phase separable hydrocarbon streamcomprising separating an aralkyl hydroperoxide cleavage mass containingsalts of neutralization into a ketone stream and a phenol streamcontaining the salts, optionally concentrating the phenol stream byfurther distillation, and forming a phase separable hydrocarbon streamby adding water at a net amount of 5 parts by weight per hour or less tothe phenol stream, optionally concentrated. While more water can beadded, as mentioned above, the net addition of water should be kept lowto avoid treating larger amounts of water downstream. More preferably,only 2 net parts by weight per hour or less, most preferably 1 part byweight per hour or less, and even 0.5 net parts by weight per hour, orless, of water needs to be added to make a phase separable hydrocarbonstream, each based on a flow of 100 parts by weight per hour of allingredients in the aralkyl hydroperoxide cleavage mass to the splitter(30). The minimum net amount of water added to the phenol stream,optionally concentrated, is an amount sufficient to phase separate aphase separable hydrocarbon stream into a hydrocarbon phase and anaqueous phase containing at least about 80 wt. % of the salts ofneutralization in less than one hour residence time.

57. Once water and the diluent are added to the crude phenolic bottomsstream to form a phase separable crude phenolic bottoms stream, theingredients are optionally but preferably thoroughly mixed. Any means ofmixing is suitable, including static mixing, turbulent in-line mixing,or agitation through a variable speed mixer, depicted in FIG. 1 as theCPC bottoms mixer (70). As shown in FIG. 1, the phase separable crudephenolic bottoms stream enters the CPC bottoms mixer (70) through line(64) to provide sufficient mixing to contact the diluent with as muchwater as possible, thereby transferring phenol solubilized in the waterphase into the hydrocarbon phase. If desired, the stream may bemicro-emulsified. The well mixed stream then enters the bottoms phaseseparator (80) through line (71).

58. In one embodiment of the invention, the composition of the phaseseparable crude phenolic bottoms stream entering the separator (80)comprises at least 40 wt. % water, less than 20 wt. % phenoliccompounds, alkali metal salts in an amount of at least 1.5 wt. %,phenolic tars, and α-methyl styrene dimers, wherein the volume ratio ofwater to all ingredients in the composition other than water is 3:1 orless. In a more preferred embodiment, the composition of the phaseseparable crude phenolic bottoms stream comprises 50 wt. % or more ofwater, greater than 5 wt. % cumene, greater than 0.5 wt. % AMS, lessthan 10 wt. % phenol, phenolic tars present in an amount of less than 8wt. %, and AMSd present in an amount of less than 5 wt. %. In a mostpreferred embodiment, the weight range of ingredients in the phaseseparable crude phenolic bottoms composition is as follows: AMS: 0.5-8wt. % Cumene: 5-15 wt. % Phenol: 3-10 wt. % AP: 3-10 wt. % DMBA: 0.2-4wt. % CP: 3-10 wt. % AMSd: 1-5 wt. % Tars/Heav: 3-8 wt. % Salts: 2-5 wt.% Water: 50-75 wt. %

59. Any means of phase separating the hydrocarbon phase from the aqueousphase in the phase separable crude phenolic bottoms stream is suitable.As depicted in FIG. 1, there is provided a bottoms phase separatorvessel (80) wherein the phase separable crude phenolic bottoms stream isinjected as a spray into one end of the vessel and allowed to phaseseparate by settling and flotation over time without agitation into thehydrocarbon phase and aqueous phase.

60. While the temperature and pressure within the bottoms phaseseparator (80) may be advantageously lowered compared to the up-streamtemperature and pressure conditions in order to promote phaseseparation, the temperature desirably remains above 100° C. to keep theviscosity of the liquid composition low and preferably to provide anoptimal density gradient between the hydrocarbon phase and the aqueousphase. Thus, temperatures exceeding the boiling point of water arepreferred, especially temperatures above 110° C., most preferably from115° to 140° C. The pressure inside the vessel should be keptsufficiently high to retain the composition in a liquid phase when thetemperatures exceed the boiling point of any ingredient at atmosphericpressure. Preferably, the pressure is set from 2 psig to 100 psig, mostpreferably from 35 psig to 70 psig. The residence time within theseparator depends upon the composition of the stream and the conditionsinside the separator In general, a residence time of 5 to 60 minutes issufficient to effectuate phase separation.

61. Since the process of the invention does not require a phaseseparator to process large quantities of feed to separate and discharge80 wt. % or more of the salts of neutralization from the phase separatoras a salty aqueous purge stream, the vessel can be advantageously sized.In particular, at least 80 wt. % of the salts of neutralization can beremoved from the process in a vessel sized at only 5000 gallons or less,even 3500 gallons or less, based on a cleavage mass feed of 100 parts byweight per hour to the splitter (30).

62. Once the aqueous phase is separated from the hydrocarbon phase, itis withdrawn as a bottoms stream through line (82), and the less denseupper layer hydrocarbon stream is withdrawn from the bottoms phaseseparator through line (81) to the heavy ends cracker (90). Throughphase separation, the amount of salts of neutralization present in thehydrocarbon phase is reduced compared to the amount of salts ofneutralization present prior to phase separation, or the amount of saltspresent in the neutralized aralkyl hydroperoxide cleavage mass stream orthe crude phenolic stream. In one embodiment, at least 80%, morepreferably at least 90 wt. %, of the salts present in the crude phenolicbottoms stream are removed from the hydrocarbon phase and transferred tothe aqueous phase. As much a 94 wt. % or more of the salts ofneutralization are removed from the process of the invention as a saltyaqueous purge stream.

63. At least a portion of the aqueous stream separated from thehydrocarbon phase is purged from the process as a waste stream fortreatment if necessary. Preferably, a portion of the aqueous phase isrecirculated through line (82) to line (62) or (63) and used as thewater source, along with a fresh feed of water in line (84) to make upfor water lost through the salt water purge, for addition to the crudephenolic bottoms stream, and another portion of the aqueous phase ispurged as a salt water purge through line (83).

64. An advantage of the process of the invention is that the amount ofwater containing salts of neutralization discharged at any stepdownstream from the stripping column is low while simultaneouslyremoving substantial amounts of salts of neutralization from theprocess. In particular, the process of the invention enables one todischarge and purge a net amount of an aqueous phase containing salts ofneutralization at a rate of less than 5 parts by weight per hour basedon 100 parts by weight per hour of the aralkyl hydroperoxide cleavagemass stream. Even at this low discharge rate, at least 80 wt. %,preferably 90 wt. % or more, of the salts of neutralization present atany stage from the aralkyl hydroperoxide cleavage mass streamcomposition immediately prior to entry into the splitter forward areremoved. In a more preferred embodiment, the net amount of aqueous phasedischarged is less than 1.5 parts by weight per hour, and even less than1, more preferably less than 0.5, and most preferably less than 0.3parts by weight per hour each based on 100 parts by weight per hour ofthe aralkyl hydroperoxide cleavage mass stream composition immediatelyprior to entry into the splitter. Accordingly, the process consumes onlysmall quantities of waste water, leading to other advantages including areduction in the amount of water that must be treated and a reduction inthe amount of phenol lost to a water purge. The removal of salts ofneutralization in the process of the invention is also not dependent onthe stability of the composition profile throughout the splitter column.

65. The process according to the invention also concentrates the amountof salt in the salty aqueous purge stream (83). The process according tothe invention can achieve salt concentrations of at least 3 wt. % in atleast 90 wt. % water, more preferably at least 4 or even at least 5 wt.% of salts of neutralization based on the weight of the salty aqueouspurge stream. A typical composition of the purge aqueous stream in line(83) comprises 90-95 wt. % water, 3-7 wt. % salts of neutralization, and0.5-3 wt. % of phenol.

66. The hydrocarbon stream in line (81) is introduced into a heavy endscracker (90) where the hydrocarbon stream is separated into a light endsstream enriched in phenolic compounds over the phase separatedhydrocarbon stream, and a tarry stream enriched in tars over the phaseseparated hydrocarbon stream, wherein the tarry stream has a reducedamount of salts of neutralization relative to the crude phenolic stream.The cracker may optionally generate light ends which are included in thelight ends stream enriched in phenolic compounds.

67. The hydrocarbon phase exiting as a stream through line (81) has atypical composition comprising: AMS: 3-10 wt. % Cumene: 10-40 wt. %Phenol: 5-25 wt. % AP: 7-20 wt .% DMBA: 1-5 wt. % CP: 7-20 wt. % AMSd:3-10 wt .% Tars/Heav: 6-20 wt. % Salts 0.005-0.02 wt. %

68. Heavy ends such as un-cracked AP, CP, AMSd, and tars/heavies, and avery small amount of phenol are removed from the bottoms of the heavyends cracker (90). Since the amount of salts are low, fouling of bottomsof the heavy ends cracker is substantially reduced. Further, fouling ofthe reboilers which re-circulate a portion of the heavy ends crackerbottoms stream back to the heavy ends cracker, as well as fouling ofother equipment for treating the heavy bottoms tar stream exitingthrough line (92), is substantially reduced. Accordingly, the heavy endsbottom stream exiting the heavy ends cracker is usable as fuel forboilers. Lighter ends in the hydrocarbon stream such as AMS, cumene,phenol, water, and the cracked products of DMBA, CP, AMSd, andtars/heavy oligomers, exit the heavy ends cracker as an overhead throughline (91).

69. In another embodiment of the invention, at least a portion of thelight ends stream is recirculated back to the neutralization zone wherethe aralkyl hydroperoxide cleavage mass is neutralized. This ispreferably accomplished by first purifying the lighter ends stream. Thelighter ends composition is fed through line (91) to a rectifier (100).Very light ingredients such as benzene, propane, and water are removedfrom the overhead of the rectifier through line (101), while higherboiling compounds such as phenol, cumene, and AMS, and minor amounts ofethyl benzene exit the bottoms of the rectifier through line (102), atleast a portion or all of which is recycled back to the neutralizer (10)through line (1). This will further enhance the ability of thecomposition in line 1 to phase separate in vessel (20) once neutralized,partially or wholly, in neutralizer (10).

What is claimed:
 1. A process for the manufacture of phenolic compoundscomprising: a) separating a neutralized aralkyl hydroperoxide cleavagemass stream containing salts of neutralization into a crude ketonestream and a crude phenolic stream containing the salts ofneutralization; b) separating the crude phenolic stream into aconcentrated phenolic-rich stream, enriched in phenolic compounds, and acrude phenolic bottoms stream enriched in tars and alpha methyl styrenedimers, each compared to the crude phenolic stream, said crude phenolicbottoms stream containing salts of neutralization; c) to the crudephenolic bottoms stream, adding water and a diluent composition, therebyforming a phase separable crude phenolic bottoms stream, said diluentcomposition comprised of hydrocarbons phase compatible with the crudephenolic bottoms stream and having a combined density lower than thedensity of the crude phenolic bottoms stream; d) separating theseparable crude phenolic bottoms stream into a hydrocarbon phase and anaqueous phase containing salts of neutralization; whereby the amount ofsalts of neutralization in the hydrocarbon phase is reduced compared tothe amount of salts of neutralization present prior to separation. 2.The process of claim 1 , wherein the weight ratio of diluent compositionto crude phenolic bottoms stream is at least 0.15:1.
 3. The process ofclaim 2 , wherein the weight ratio of diluent composition to crudephenolic bottoms stream is at least 0.3:1.
 4. The process of claim 1 ,wherein the volume ratio of water to crude phenolic bottoms stream is atleast 1:1.
 5. The process of claim 1 , comprising: (i) adding thediluent composition to the crude phenolic bottoms stream thereby forminga diluted crude phenolic bottoms stream, and (ii) subsequently mixingwater to the diluted crude phenolic bottoms stream, thereby forming aseparable crude phenolic bottoms stream.
 6. The process of claim 5 ,wherein the ratio of diluent to crude phenolic bottoms stream is atleast 0.3:1, and the volume ratio of water to diluted crude phenolicbottoms stream ranges from 1.5:1 to 3:1.
 7. The process of claim 6 ,wherein the diluent composition comprises less than 20 wt. % of phenoliccompounds.
 8. The process of claim 7 , wherein the diluent compositioncomprises cumene and α-methyl styrene.
 9. The process of claim 6 ,further comprising: (i) separating said crude ketone stream into aconcentrated ketone-rich stream, enriched in ketone over the crudeketone stream, and a crude ketone bottoms stream; (ii) feeding at leasta portion of the crude ketone bottoms stream as said diluent compositionto the crude phenolic bottoms stream in step c).
 10. The process ofclaim 9 , further comprising feeding a portion of said crude ketonebottoms stream to a neutralization zone for neutralization of a aralkylhydroperoxide cleavage mass.
 11. The process of claim 6 , wherein aportion of said aqueous phase in step d) is recirculated and used as thewater in step cii), and a portion of the aqueous phase is purged as asalt water purge.
 12. The process of claim 11 , wherein the salt waterpurge contains at least 80 wt. % of salts present in the crude phenolicbottoms stream.
 13. The process of claim 6 , wherein at least 90% of thesalts present in phase separable crude phenolic bottoms stream prior toseparation are removed from said hydrocarbon phase.
 14. The process ofclaim 1 , wherein said separation in step d) is conducted in a phaseseparation vessel at a temperature above 110° C. and a pressuresufficient to keep the separable crude phenolic bottoms stream in theliquid phase.
 15. The process of claim 1 , further comprising: (e)separating said hydrocarbon stream into a light ends stream, enriched inphenolic compounds, and a tarry stream enriched in tars, said tarrystream having a reduced amount of salts of neutralization relative tothe crude phenolic stream.
 16. The process of claim 15 , wherein atleast a portion of said light ends stream is re-circulated to aneutralization zone in which an aralkyl hydroperoxide cleavage mass isneutralized.
 17. A process for the manufacture of phenolic compoundscomprising wholly or partially neutralizing a aralkyl hydroperoxidecleavage mass containing an acid and having a pH of less than 6 in theneutralization zone, thereby forming an aqueous neutralized aralkylhydroperoxide cleavage mass containing salts of neutralization,subsequently separating said aqueous neutralized aralkyl hydroperoxidecleavage mass into an aqueous stream and a neutralized aralkylhydroperoxide cleavage mass stream containing a smaller amount of saltsthan in the aqueous stream, subsequently separating the aralkylhydroperoxide cleavage mass into a crude ketone stream and a crudephenolic stream containing the salts, separating said crude acetonestream into a concentrated ketone rich stream and a crude ketone bottomsstream, separating said crude phenolic stream into a concentratedphenolic-rich stream and a crude phenolic bottoms stream, separating thecrude phenolic bottoms stream into a light ends stream and a tarrystream containing an amount of salts reduced by at least 90% of theamount of salts contained in the crude phenolic bottoms stream, andrecycling at least a portion of said crude ketone bottoms stream and atleast a portion of said light ends stream as feeds to said aralkylhydroperoxide cleavage mass, said aqueous neutralized aralkylhydroperoxide cleavage mass, or to both.
 18. The process of claim 17 ,wherein at least a portion of said crude ketone bottoms stream and atleast a portion of said light ends stream are recycled to said aralkylhydroperoxide cleavage mass prior to neutralization.
 19. A compositioncomprising at least 40 wt. % water, less than 20 wt. % phenoliccompounds, alkali metal salts in an amount of at least 1.5 wt. %,phenolic tars, and α-methyl styrene dimers, wherein the volume ratio ofwater to all ingredients in said composition other than water is between1:1 and about 3:1.
 20. The composition of claim 19 , comprising 50 wt. %or more of water, greater than 5 wt. % cumene, greater than 1 wt. %α-methyl styrene, less than 10 wt. % phenol, phenolic tars present in anamount of less than 6 wt. %, and α-methyl styrene dimers present in anamount of less than 4 wt. %.
 21. The process of claim 1 , wherein all ora portion of the aqueous stream is purged as an aqueous purge streamfrom the process, and the total amount of the aqueous purge streamcontaining salts of neutralization is less than 5 parts by weight perhour based on 100 parts by weight per hour of the aralkyl hydroperoxidecleavage mass stream.
 22. The process of claim 21 , wherein the netamount of aqueous purge stream discharged from the process is less than1 part by weight per hour.
 23. A process for removing salts ofneutralization present in a partially or wholly neutralized aralkylhydroperoxide cleavage mass comprising removing 80 wt. % or more of saidsalts from said cleavage mass through one or more aqueous streamsdischarged and purged from said process, the combined flow rate of allaqueous purged stream(s) containing the salts being less than 5 parts byweight per hour based on a flow rate of 100 parts by weight per hour ofsaid cleavage mass fed to a means for separating said cleavage mass intoa crude ketone stream and a crude phenolic stream.
 24. The process ofclaim 23 , wherein at least 90 wt. % of the salts are removed, and theflow rate of the aqueous discharge stream(s) is less than 1 part byweight per hour.
 25. The process of claim 23 , wherein the flow rate ofthe aqueous discharge stream(s) is less than 0.5 parts by weight perhour.
 26. The process of claim 23 , wherein said aralkyl hydroperoxidecomprises cumene hydroperoxide, said ketone comprises acetone, saidphenolic comprises phenol, and said salt comprises an alkali metalsulfate.
 27. A process for manufacturing phenolic compounds comprisingfeeding a wholly or partially neutralized aralkyl hydroperoxide cleavagemass containing salts of neutralization to a splitter, separatingacetone and phenol from said cleavage mass in the splitter, removing allor a portion of the phenol from the splitter, followed by feeding saidall or a portion of said phenol to a phase separation vessel having avolume of 5000 gallons or less, based on 100 parts by weight per hour ofcleavage mass feed to the splitter, and removing at least 80 wt. % ofthe salts of neutralization from said phenol.
 28. The process of claim27 , wherein the size of the separation vessel is 3500 gallons or less.29. A process for removing salts of neutralization, comprising feedingan aralkyl hydroperoxide cleavage mass containing salts ofneutralization to a splitter, separating acetone from a crude stream ofphenol in said splitter, followed by feeding a portion or all of saidcrude phenol stream to a phase separator as a feed comprisinghydrocarbons, water, and salts of neutralization, the total amount ofhydrocarbon feed from any source to said separator being less than 10parts by weight per hour, based on 100 parts by weight per hour of saidcleavage mass fed to the splitter, wherein at least 80 wt. % of thesalts of neutralization are removed from the crude phenol stream. 30.The process of claim 29 , wherein the total amount of hydrocarbon feedto the phase separator is less than 7 parts by weight per hour.
 31. Theprocess of claim 30 , wherein the total amount of hydrocarbon feed tothe phase separator is 5 parts by weight per hour or less, and whereinat least 90 wt. % of the salts of neutralization are removed from thecrude phenol stream.
 32. A process for removing salts of neutralizationfrom an aralkyl hydroperoxide cleavage mass containing salts ofneutralization comprising separating acetone from said cleavage mass,followed by purging the salts of neutralization in an aqueous purgestream comprising at least 3 wt. % of the salts of neutralization and atleast 90 wt. % water, based on the weight of the purge stream.
 33. Theprocess of claim 32 , wherein the aqueous purge stream comprises atleast 4 wt. % of salts of neutralization.
 34. A process for makingphenol comprising feeding an aralkyl hydroperoxide cleavage masscontaining salts of neutralization into a splitter and separating thecleavage mass in the splitter into a ketone stream and a phenol streamcontaining the salts, optionally concentrating the phenol stream byfurther distillation, and forming a phase separable hydrocarbon streamfrom said phenol stream comprising adding a net amount of water of 5parts by weight per hour or less to the phenol stream, based on 100parts by weight per hour of cleavage mass fed to the splitter, phaseseparating the phase separable hydrocarbon stream into an aqueous streamand a hydrocarbon stream, and discharging a portion or all of theaqueous stream from the process as an aqueous purge stream, wherein atleast 80 wt. % of the salts of neutralization present in the cleavagemass entering the splitter are removed through said purge stream. 35.The process of claim 34 , wherein the net amount of water added is 2parts by weight per hour or less.
 36. The process of claim 35 , whereinthe net amount of water added is 1 part by weight per hour or less. 37.The process of claim 36 , wherein the net amount of water added is 0.5parts by weight per hour or less.
 38. The process of claim 37 , whereinat least 90 wt. % of the salts of neutralization are removed throughsaid purge stream.